Diaminonitropropiophenones and process of preparation



DIAMINONITROPROPIOPHENONES AND PROCESS OF PREPARATION Carlo Giuseppe Albcrti and Alberto Vercellone, Milan,"

Italy, poration of Italy No Drawing. Filed Dec. 10, 1957, Ser. No. 701,736

Claims priority, application Italy Apr. 29, 1954 4 Claims. (Cl. 260-247 .2)

This invention relates to new synthetic products and to a process for their preparation. This application is a continuation-impartof application Serial No. 504,340, filed April 27, 1955, now abandoned.

More particularly, the invention relates to a-acylaminofl-aminonitropropiophenones, having the general for mula NHCOR R:

wherein R represents a lower alkyl or dihaloalkyl and R and R individually represent a lower alkyl and jointly with the nitrogen to which they are bound-a saturatedheterocyclic ring"whi ch may contain an oxygen atom.

These compounds have been 'found to be important .because of their pronounced antiseptic properties. In

particular they have, in numerous in vitro? tests, shown a fungicidal activity against many varieties of fungi, both of the plant and of the animal parasite type. They may be applied to combat fungi on animal organism in the usual forms of "ointments, solutions etc., while for agricultural uses they may be conveniently dilutedwith inert solid carriers for dusting, or in solution or emulsion "j prepared by means of inert liquid materialsfor spraying:

According to this invention, the'process of synthesizing these compounds consists in adding one mol of an u-acylamino-nitroacrylophenone of the formula Nncon' wherein R is a lower alkyl or dihaloalkyl to one moloi a secondary amine, having the general formula wherein R and R individually represent a lower alkyl and jointly with the nitrogen to which they are bound .a saturated heterocyclicring which may contain an oxygenatom. v ,1 i The materials are reacted intstoichiomet'ri'c ratio,-:in the presence of an inert solvent, such as aliphatic and aromatic hydrocarbons esters, alcohols or ethers, and

at temperatures ranging from about to. about;l00 C.

As set forth in the vcopending.application Serial No;-

603,181 of August 9; i956, the aracylaminonitroacrylophenone starting material is obtained by oxidizing. N, O diacyl derivatives of the nitrophenyl' amino-propanediols l 'ajtented Apr. 18, 1961 ICC.

r to form a-acylamino-fi-acyloxy-propiophenones and eliminating {the acyloxy group in p-position, in the form of an acid, due to the union with the hydrogenin a-position.

assignors to Societa Farmaceutici Italia, a cor- H HCOR olNO-oo c' momoo on NHCOR Nnooorron EXAMPLE 2 t 11.3 g. of p-nitro-a-dichloroacetamino-acrylophenone and 1.67 g. of dimethylamine are kept in benzene, at room temperature, for 1 5 to 18 hours. After that time,

12.15 g. of p.mtro-a dichloroacetamino-fidimethylamino needles meltingat propiophenone, in the form of yellow 94-95 'C., are filtered otf.

co-oH-fom-N NHCOOHCI: on,

EXAMPLE, 3

' 12.0 g. of p-nitro-a-dichloroacetamino-acrylophenone and 3.3 g. of piperidine in benzene are stirred at room temperature. 'After 15 to -18 hours the solventis re-,

moved by evaporation and the residue recrystallized from benzene-petroleum ether. 9.95 g. of p nitro-a dich1oroacetamino-)8 piperidine-propiophenone are obtained in a form of yellow dust. v

NorO oo-on-om-N -onr-onz-jgon, I i i I 'F HcooHm,

All "co pounds described n; the a assshow in 'v1tro ,(ager-potato medium) a fungicidal activity.

1 Iable I illustrates the minimum growth inhibitory doses in 7/66. of the herein-claimed compounds incon nection with Alternaria solani, Aspergillqs niger, Candida albicans and Penicillium notatum.

3. p.nitro 04 dichloroacetamino 13 (piper-Mus)- propiophenone Table 1 Compounds Fungicidal activity NOz-COCHOH: Penicil- V Alter-norm Aspergillus Candida lzum NHCOGHC], sulam m'qer albuana notutum (R radical) V (1) CHr- CH In, a V r R- an 100 60 cm-ca R-N 12 400 1 40o Hz-CH: R N cH, v 12 600 25 500 oflr-ci" Compounds 1, 2 and 3 are the products described in Examples 1, 2 and 3. v NOa-QO 0-0H- cH,-N -cH2-'cm)cm Moreover, p-nitro-u-dichloroacetamino-p-(4-morpholyl ni1)-propiophenone. in a concentration of 100 'y/cc; in Sabou-raud'medium shows growth inhibiting'action against the followingiungi: Debaryomyces canelnsis, D. guillcrmondi, D hudeloi, D. marylana'ii, D. neoformans, D. tyrocola, Epidermophyton"interdigitale, Glenospora graphii, Glenosporella a'ermatitidis, H istoplasma capsulatum, Pseudomycodei'ma metalense, T orulopsis ncoformans, T ric0- phyton teggini, T. plicatil, Actinomyces nostrb'mi Vitz. and Nocardia esteroides.

We claim:

1. p.nitro a dichldrdacetamino B (4 morpholinyl) -propiophenone NOI-O-C o-c am-cni-m-cm-cmho 24 1mm 5a P diohloroacetamino 8 dimethylaminoe propiophe 10ne;.;; V a

1 770,498 v -'Grat-Britain' Mar. 20, 1957 NOI-O-C ocH-oHr-N v l NHOOR- m in'which'R isa member of the group consisting of lower 7 alkyl and 1 dihalo lower alkyl, and the' radical R2 is taken fromthe group' consisting of'di-lower alkyl amine and radicals in which R and R are joined to form, with the; attached nitrogen atom', a radical of the group consisting of morphoilino and piperidind.

IReferen ces Cited in the file of thispatent FOREIGN PATENTS OTHER REFERENCES Degering: An Outline of Organic Nitrogen Compound-s (1945), p. 305.

Larramona:

com tjiand, ,vol.' 238, pp. 488-490" 

1. P NITRO - A - DICHLOROACETAMINO - B - (4 - MORPHOLINYL)-PROPIOPHENONE
 4. A COMPOUND OF THE FORMULA 